High impact strength 3d printing materials derived from polycycloolefin monomers and crosslinkers

ABSTRACT

Embodiments in accordance with the present invention encompass a composition containing a latent catalyst and a compound capable of generating a Bronsted acid with a counterion capable of coordinating and activating the latent catalyst along with one or more monomers which undergo ring open metathesis polymerization (ROMP) and one or more multi-functional crosslinkable molecules when said composition is exposed to a suitable radiation forms a three-dimensional (3D) object. The catalyst system employed therein can be sensitive to oxygen and thus inhibits polymerization in ambient atmospheric conditions. The three-dimensional objects made by this process exhibits improved mechanical properties, particularly, high distortion temperature, impact strength, elongation to break, among others. Accordingly, compositions of this invention are useful as 3D inkjet materials for forming high impact strength objects of various sizes with microscale features lower than 100 microns, among various other uses.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/724,600, filed Dec. 23, 2019, now allowed, which claims the benefitof U.S. Provisional Application No. 62/783,347, filed Dec. 21, 2018, andU.S. Provisional Application No. 62/830,867, filed Apr. 8, 2019, all ofwhich are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION Field of the Invention

Embodiments in accordance with the present invention relate generally toa single component composition containing mass polymerizablepolycycloolefin monomer(s), crosslinkers and a catalyst which isactivated photolytically by a compound capable of generating Bronstedacid with a counterion capable of coordinating and activating the latentcatalyst useful as three-dimensional (3D) printing materials. Thecompositions so formed exhibit high mechanical properties, specificallyexhibiting high impact strength having utility in a variety ofapplications including as 3D ink compositions, among other uses. Morespecifically, this invention relates to room temperature stable singlecomponent compositions encompassing norbornene (NB) anddicyclopentadiene (DCPD) based olefinic monomers and an oxygen sensitivecatalyst system which is activated under photolytic conditions therebyundergoing mass polymerization to form solid objects, including films,vias, patterned lines, among others.

Description of the Art

Recently there has been an increased interest in developing 3D inkcompositions which can produce 3D objects having finer structures atmicron levels. A few of the recently introduced 3D ink systems arecapable of continuous production of 3D objects which are useful in avariety of diversified applications including for example tissueengineering to electronic components. See for example, J. M. DeSimone etal., Science, Vol. 347, pp 1349-1352 (2015), where it is disclosed acontinuous liquid interface production (CLIP), which is controlled by a“dead zone” to avoid any oxygen sensitivity of the 3D ink materialsemployed therein, which allows fabrication of a series of objects atmuch faster speed and with high resolution such that the objects soformed can feature patterns in the 50 to 100 micron range.

WO2017/068590 A1 discloses a series of 3D inkjet printing materialsusing dicyclopentadiene compounds polymerizable by ring-openingmetathesis polymerization methods.

U.S. Pat. No. 9,909,022 B2 discloses various ink compositions which whenprinted and cured forms organic thin films on a substrate. Such inkcompositions are contemplated to be used in organic light emitting diode(OLED) displays. The compositions disclosed therein are generallycurable polyethylene glycol acrylates and polyol acrylates, which areknown to be not stable at temperatures higher than 200° C.

Accordingly, there is still a need for developing 3D printing materialsthat can be cured at a faster speed and exhibit desirable thermal andmechanical properties for fabricating industrially useful 3D objects,films and patterned features at a lower cost.

Thus, it is an object of this invention to provide 3D printingcompositions that overcome the gaps faced by the art. More specifically,it is an object of this invention to provide a single componentcomposition that will mass polymerize rapidly under inert atmospheres toform 3D objects under the conditions of 3D printing system. It isfurther an object of this invention to provide stable single componentmass polymerizable composition with no change in viscosity at or belownormal storage conditions but which undergoes mass polymerization onlyunder the 3D process conditions producing solid objects featuring veryhigh impact strength.

Other objects and further scope of the applicability of the presentinvention will become apparent from the detailed description thatfollows.

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that by employing a single componentfiller composition, it is now possible to form three dimensional objectshaving improved thermal and mechanical properties, most notably thecompositions of this invention can be tailored to desirablethermo-mechanical properties. For example, the compositions of thisinvention can be tailored to exhibit glass transition temperatures(T_(g)) higher than 150° C., high heat distortion temperature (HDT,higher than 50° C. at 1.82 MPa/264 psi), high elongation to break(greater than 100 percent), high impact strength (Izod impact strengthof about 100 J/m or higher) and high tensile strength (greater than 50MPa). It is also important to note that the compositions of thisinvention can be mass polymerized under photolytic conditions at afaster speed and thus can be employed in any of the 3D technologies,including layer by layer approach, inkjet formulations and in thestereolithographic applications involving continuous liquid interfaceproduction of 3D objects. The compositions of this invention areexpected to exhibit faster photopolymerizing capabilities thus enablingto form a wide variety of objects of different sizes, including sizesgreater than 10 inches and structural details lower than 50 μm. Further,compositions of this invention are also expected to exhibit lowshrinkage due to their rigid polycycloolefinic structure. In addition,as the components of this invention undergo fast mass polymerizationupon application they do not leave behind any fugitive small moleculeswhich needs further processing. Generally, no other small moleculeadditives need to be employed thus offering additional advantages. Mostimportantly, the compositions of this invention are stable (i. e., nochange in viscosity) at ambient atmospheric conditions including up to35° C. for several hours to days, and undergo mass polymerization onlyunder photolytic conditions.

Accordingly, there is provided a single component compositionencompassing:

a) one or more monomers of formula (I):

wherein:

m is an integer 0, 1 or 2;

is a single bond or a double bond;

R₁, R₂, R₃ and R₄ are the same or different and each independentlyselected from the group consisting of hydrogen, halogen, methyl, ethyl,linear or branched (C₃-C₁₆)alkyl, (C₂-C₁₆)alkenyl,perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, methoxy, ethoxy, linear or branched(C₃-C₁₆)alkoxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, (C₆-C₁₄)aryl,(C₆-C₁₄)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₄)aryl,perfluoro(C₆-C₁₄)aryl(C₁-C₃)alkyl, (C₆-C₁₄)aryloxy,(C₆-C₁₄)aryl(C₁-C₆)alkoxy, tri(C₁-C₆)alkoxysilyl and a group of formula(A):

—Z-Aryl  (A)

wherein:

Z is a bond or a group selected from the group consisting of:

(CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O, (CR₅R₆)_(a)—O—(CR₅R₆)_(b),(CR₅R₆)_(a)—O—(SiR₅R₆)_(b), (CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b),(CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b), (CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a andb are integers which may be the same or different and each independentlyis 1 to 12;

R₅ and R₆ are the same or different and each independently selected fromthe group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₆)alkyl, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy,(C₂-C₆)acyl, (C₂-C₆)acyloxy, phenyl and phenoxy;

Aryl is phenyl or phenyl substituted with one or more of groups selectedfrom the group consisting of methyl, ethyl, linear or branched(C₃-C₆)alkyl, hydroxy, methoxy, ethoxy, linear or branched(C₃-C₆)alkyloxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, phenyl and phenoxy; or

one of R₁ or R₂ taken together with one of R₃ or R₄ and the carbon atomsto which they are attached to form a (C₅-C₇)carbocyclic ring optionallycontaining one or more double bonds;

b) optionally one or more monomers of formula (IV):

wherein

R₁₆ and R₁₇ are the same or different and each independently selectedfrom the group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₆)alkyl, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy,acetoxy, (C₂-C₆)acyl, phenyl and phenoxy; or

R₁₆ taken together with R₁₇ and the carbon atoms to which they areattached to form a (C₅-C₇)carbocyclic ring optionally containing one ormore double bonds;

R₁₈ is hydrogen, halogen, methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, hydroxy, methoxy,ethoxy, linear or branched (C₃-C₁₆)alkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, —O(CO)R₁₉ and —O(CO)OR₁₉, where R₁₉ ismethyl, ethyl, linear or branched (C₃-C₁₆)alkyl, (C₆-C₁₀)aryl and(C₆-C₁₀)aryl(C₁-C₆)alkyl;

c) optionally one or more compounds selected from the group consistingof:

-   -   i) a compound of formula (VIIa):

-   -   ii) a compound of formula (VIIb):

and

-   -   iii) a compound of formula (VIIc):

where

m is an integer 0, 1 or 2;

b is an integer from 1 to 10;

K is selected from the group consisting of CH₂, CH₂—CH₂, O and S;

X is selected from the group consisting of O, S, NR_(a), SiR_(b)R_(c),SiR_(b)R_(c)O(SiR_(b)R_(c)O)_(n)SiR_(b)R_(c),SiR_(b)R_(c)(C₆-C₁₀)arylSiR_(b)R_(c), —C(O)—, —C(O)O—, —OC(O)—,—OC(O)—O—, —S—C(O)—, —C(O)—S—, —CH═CH— and —C≡C—;

R_(a), R_(b) and R_(c) are independently of each other selected from thegroup consisting of hydrogen, methyl, ethyl or a linear or branched(C₃-C₁₂)alkyl, (C₃-C₈)cycloalkyl, (C₅-C₁₂)bicycloalkyl,(C₅-C₁₂)bicycloalkenyl and (C₅-C₁₂)bicycloalkenyl(C₁-C₃)alkylSi(CH₃)₂,and such that O, NR_(a) and/or S atoms are not linked directly to oneanother; and

n is an integer from 0 to 10;

d) a latent organo-transition metal catalyst comprising a metal selectedfrom the group consisting of ruthenium and osmium; and

e) a compound capable of releasing a Bronsted acid when subjected tophotolytic conditions; and wherein

said composition is in a clear liquid form at room temperature.

In another aspect of this invention there is also provided a kitencompassing the composition of this invention for forming a threedimensional object.

DETAILED DESCRIPTION

The terms as used herein have the following meanings:

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Since all numbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used herein and in the claimsappended hereto, are subject to the various uncertainties of measurementencountered in obtaining such values, unless otherwise indicated, allare to be understood as modified in all instances by the term “about.”

Where a numerical range is disclosed herein such range is continuous,inclusive of both the minimum and maximum values of the range as well asevery value between such minimum and maximum values. Still further,where a range refers to integers, every integer between the minimum andmaximum values of such range is included. In addition, where multipleranges are provided to describe a feature or characteristic, such rangescan be combined. That is to say that, unless otherwise indicated, allranges disclosed herein are to be understood to encompass any and allsub-ranges subsumed therein. For example, a stated range of from “1 to10” should be considered to include any and all sub-ranges between theminimum value of 1 and the maximum value of 10. Exemplary sub-ranges ofthe range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8,and 5.5 to 10, etc.

As used herein, the expression “alkyl” means a saturated, straight-chainor branched-chain hydrocarbon substituent having the specified number ofcarbon atoms. Particular alkyl groups are methyl, ethyl, n-propyl,isopropyl, tert-butyl, and so on. Derived expressions such as “alkoxy”,“thioalkyl”, “alkoxyalkyl”, “hydroxyalkyl”, “alkylcarbonyl”,“alkoxycarbonylalkyl”, “alkoxycarbonyl”, “diphenylalkyl”, “phenylalkyl”,“phenylcarboxyalkyl” and “phenoxyalkyl” are to be construed accordingly.

As used herein, the expression “cycloalkyl” includes all of the knowncyclic groups. Representative examples of “cycloalkyl” includes withoutany limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, and the like. Derived expressions such as“cycloalkoxy”, “cycloalkylalkyl”, “cycloalkylaryl”, “cycloalkylcarbonyl”are to be construed accordingly.

As used herein, the expression “perhaloalkyl” represents the alkyl, asdefined above, wherein all of the hydrogen atoms in said alkyl group arereplaced with halogen atoms selected from fluorine, chlorine, bromine oriodine. Illustrative examples include trifluoromethyl, trichloromethyl,tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl,pentabromoethyl, pentaiodoethyl, and straight-chained or branchedheptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl,nonachlorobutyl, undecafluoropentyl, undecachloropentyl,tridecafluorohexyl, tridecachlorohexyl, and the like. Derivedexpression, “perhaloalkoxy”, is to be construed accordingly. It shouldfurther be noted that certain of the alkyl groups as described herein,such as for example, “alkyl” may partially be fluorinated, that is, onlyportions of the hydrogen atoms in said alkyl group are replaced withfluorine atoms and shall be construed accordingly.

As used herein the expression “acyl” shall have the same meaning as“alkanoyl”, which can also be represented structurally as “R—CO—,” whereR is an “alkyl” as defined herein having the specified number of carbonatoms. Additionally, “alkylcarbonyl” shall mean same as “acyl” asdefined herein. Specifically, “(C₁-C₄)acyl” shall mean formyl, acetyl orethanoyl, propanoyl, n-butanoyl, etc. Derived expressions such as“acyloxy” and “acyloxyalkyl” are to be construed accordingly.

As used herein, the expression “aryl” means substituted or unsubstitutedphenyl or naphthyl. Specific examples of substituted phenyl or naphthylinclude o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl,2-methylnaphthyl, etc. “Substituted phenyl” or “substituted naphthyl”also include any of the possible substituents as further defined hereinor one known in the art.

As used herein, the expression “arylalkyl” means that the aryl asdefined herein is further attached to alkyl as defined herein.Representative examples include benzyl, phenylethyl, 2-phenylpropyl,1-naphthylmethyl, 2-naphthylmethyl and the like.

As used herein, the expression “alkenyl” means a non-cyclic, straight orbranched hydrocarbon chain having the specified number of carbon atomsand containing at least one carbon-carbon double bond, and includesethenyl and straight-chained or branched propenyl, butenyl, pentenyl,hexenyl, and the like. Derived expression, “arylalkenyl” and fivemembered or six membered “heteroarylalkenyl” is to be construedaccordingly. Illustrative examples of such derived expressions includefuran-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, and the like.

As used herein, the expression “heteroaryl” includes all of the knownheteroatom containing aromatic radicals. Representative 5-memberedheteroaryl radicals include furanyl, thienyl or thiophenyl, pyrrolyl,isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl,and the like. Representative 6-membered heteroaryl radicals includepyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the likeradicals. Representative examples of bicyclic heteroaryl radicalsinclude, benzofuranyl, benzothiophenyl, indolyl, quinolinyl,isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl,pyridothienyl, and the like radicals.

“Halogen” or “halo” means chloro, fluoro, bromo, and iodo.

In a broad sense, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a few of the specificembodiments as disclosed herein, the term “substituted” meanssubstituted with one or more substituents independently selected fromthe group consisting of (C₁-C₆)alkyl, (C₂-C₆)alkenyl,(C₁-C₆)perfluoroalkyl, phenyl, hydroxy, —CO₂H, an ester, an amide,(C₁-C₆)alkoxy, (C₁-C₆)thioalkyl and (C₁-C₆)perfluoroalkoxy. However, anyof the other suitable substituents known to one skilled in the art canalso be used in these embodiments.

It should be noted that any atom with unsatisfied valences in the text,schemes, examples and tables herein is assumed to have the appropriatenumber of hydrogen atom(s) to satisfy such valences.

By the term “latent organo-transition metal catalyst” is meantorgano-transition metal compounds that show little or no catalyticactivity at a particular (usually ambient atmospheric conditions)temperature and initiate such activity upon exposure to suitableradiation.

By the term “three dimensional object” or “3D object” means any of themacroscale or microscale objects that can be formed from thecompositions of this invention by any of the known techniques having awide variety of applications including electronic, optoelectronic, andother applications.

By the term “derived” is meant that the polymeric repeating units arepolymerized (formed) from, for example, polycyclic monomers, such asnorbornene-type monomers in accordance with formulae (I) or (IV) whereinthe resulting polymers are ring opened metathesis polymerized (ROMP),for example, the 2,3 double bond of norbornene-type monomers are ringopened and polymerized as shown below:

Accordingly, in accordance with the practice of this invention there isprovided a single component mass polymerizable composition encompassing:

a) one or more monomers of formula (I):

wherein:

m is an integer 0, 1 or 2;

is a single bond or a double bond;

R₁, R₂, R₃ and R₄ are the same or different and each independentlyselected from the group consisting of hydrogen, halogen, methyl, ethyl,linear or branched (C₃-C₁₆)alkyl, (C₂-C₁₆)alkenyl,perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, methoxy, ethoxy, linear or branched(C₃-C₁₆)alkoxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, (C₆-C₁₄)aryl,(C₆-C₁₄)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₄)aryl,perfluoro(C₆-C₁₄)aryl(C₁-C₃)alkyl, (C₆-C₁₄)aryloxy,(C₆-C₁₄)aryl(C₁-C₆)alkoxy, tri(C₁-C₆)alkoxysilyl and a group of formula(A):

—Z-Aryl  (A)

wherein:

Z is a bond or a group selected from the group consisting of:

(CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O, (CR₅R₆)_(a)—O—(CR₅R₆)_(b),(CR₅R₆)_(a)—O—(SiR₅R₆)_(b), (CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b),(CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b), (CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a andb are integers which may be the same or different and each independentlyis 1 to 12;

R₅ and R₆ are the same or different and each independently selected fromthe group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₆)alkyl, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy,(C₂-C₆)acyl, (C₂-C₆)acyloxy, phenyl and phenoxy;

Aryl is phenyl or phenyl substituted with one or more groups selectedfrom the group consisting of methyl, ethyl, linear or branched(C₃-C₆)alkyl, hydroxy, methoxy, ethoxy, linear or branched(C₃-C₆)alkyloxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, phenyl and phenoxy; or

one of R₁ or R₂ taken together with one of R₃ or R₄ and the carbon atomsto which they are attached to form a (C₅-C₇)carbocyclic ring optionallycontaining one or more double bonds;

b) optionally one or more monomers of formula (IV):

wherein

R₁₆ and R₁₇ are the same or different and each independently selectedfrom the group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₆)alkyl, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy,acetoxy, (C₂-C₆)acyl, phenyl and phenoxy; or

R₁₆ taken together with R₁₇ and the carbon atoms to which they areattached to form a (C₅-C₇)carbocyclic ring optionally containing one ormore double bonds;

R₁₈ is hydrogen, halogen, methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, hydroxy, methoxy,ethoxy, linear or branched (C₃-C₁₆)alkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, —O(CO)R₁₉ and —O(CO)OR₁₉, where R₁₉ ismethyl, ethyl, linear or branched (C₃-C₁₆)alkyl, (C₆-C₁₀)aryl and(C₆-C₁₀)aryl(C₁-C₆)alkyl;

c) optionally one or more compounds selected from the group consistingof:

-   -   i) a compound of formula (VIIa):

-   -   ii) a compound of formula (VIIb):

and

-   -   iii) a compound of formula (VIIc):

where

m is an integer 0, 1 or 2;

b is an integer from 1 to 10;

K is selected from the group consisting of CH₂, CH₂—CH₂, O and S;

X is selected from the group consisting of O, S, NR_(a), SiR_(b)R_(c),SiR_(b)R_(c)O(SiR_(b)R_(c)O)_(n)SiR_(b)R_(c),SiR_(b)R_(c)(C₆-C₁₀)arylSiR_(b)R_(c), —C(O)—, —C(O)O—, —OC(O)—,—OC(O)—O—, —S—C(O)—, —C(O)—S—, —CH═CH— and —C≡C—;

R_(a), R_(b) and R_(c) are independently of each other selected from thegroup consisting of hydrogen, methyl, ethyl or a linear or branched(C₃-C₁₂)alkyl, (C₃-C₈)cycloalkyl, (C₅-C₁₂)bicycloalkyl,(C₅-C₁₂)bicycloalkenyl and (C₅-C₁₂)bicycloalkenyl(C₁-C₃)alkylSi(CH₃)₂,and such that O, NR_(a) and/or S atoms are not linked directly to oneanother; and

n is an integer from 0 to 10;

d) a latent organo-transition metal catalyst comprising a metal selectedfrom the group consisting of ruthenium and osmium; and

e) a compound capable of releasing a Bronsted acid when subjected tophotolytic conditions; and wherein said composition is in a clear liquidform at room temperature.

As used herein the Aryl may further include the following:

substituted or unsubstituted biphenyl of formula:

substituted or unsubstituted naphthyl of formula:

substituted or unsubstituted terphenyl of formula:

substituted or unsubstituted anthracenyl of formula:

substituted or unsubstituted fluorenyl of formula:

where R_(x) in each occurrence is independently selected from methyl,ethyl, linear or branched (C₃-C₁₂)alkyl or (C₆-C₁₀)aryl.

The monomers employed in the composition of this invention arethemselves known in the literature or can be prepared by any of theknown methods in the art to make such or similar types of monomers.

In addition, the monomers as described herein readily undergo masspolymerization, i.e., substantially in their neat form without use ofany solvents when polymerized under mass ring open metathesispolymerization (ROMP) conditions using certain transition metalcatalysts, such as for example, organo-ruthenium and organo-osmiumcompounds. See for example, R. H. Grubbs et al., Handbook of Metathesis,Ed.: Wiley-VCH, Weinheim, Germany, 2003, R. H. Grubbs et al., Acc. Chem.Res. 2001, 34, 18-29, R. H. Grubbs et al., Angew. Chem. Int. Ed., 2006,45, 3760-3765. Also, see U.S. Pat. No. 6,838,489, pertinent portions ofwhich are incorporated herein by reference. The term “masspolymerization” as used herein shall have the generally accepted meaningin the art. That is, a polymerization reaction that is generally carriedout substantially in the absence of a solvent. In some cases, however, asmall proportion of solvent is present in the reaction medium. Forexample, such small amounts of solvent may be used to dissolve thelatent catalyst and/or the activator or convey the same to the reactionmedium. Also, some solvent may be used to reduce the viscosity of themonomer or to dissolve the monomer if it is in a solid form. In somecases the co-monomer, if employed, may itself serve as a solvent both toreduce the viscosity and/or to dissolve the co-monomer. The amount ofsolvent that can be used in the reaction medium may be in the range of 0to 5 weight percent based on the total weight of the monomers employed.Any of the suitable solvents that dissolves the catalyst, activatorand/or monomers can be employed in this invention. Examples of suchsolvents include alkanes, cycloalkane, toluene, THF, dichloromethane,dichloroethane, and the like.

Advantageously, it has now been found that one or more of the monomersthemselves can be used to dissolve the latent catalyst as well as theactivator and thus avoiding the need for the use of solvents. Inaddition, one monomer can itself serve as a solvent for the othermonomer and thus eliminating the need for an additional solvent. Forexample, if first monomer of formula (I) is a solid at room temperature,then the second monomer of formula (I), which is liquid at roomtemperature can be used as a solvent for the first monomer of formula(I) which is a solid or vice versa. Therefore, in such situations morethan one monomer can be employed in the composition of this invention.

Accordingly, it has now been surprisingly found that monomers of formula(I) serve as raw materials for fabricating a three dimensional (3D)objects using any of the known 3D technologies. In general, thecomposition of this invention exhibits low viscosity, which can be below100 centipoise at 25° C. and in some embodiments below 50 centipoise(cP) at 25° C. In some embodiments, the viscosity of the composition ofthis invention is less than 40 centipoise at 25° C. In some otherembodiments the viscosity of the composition of this invention is in therange from about 10 to 40 centipoise at 25° C. In yet some otherembodiments the viscosity of the composition of this invention is lowerthan 30 cP, lower than 20 cP, lower than 15 cP, lower than 12 cP at 25°C. In some embodiments it may be lower than 10 cP at 40° C. In someembodiments the viscosity of the composition of this invention is in therange from about 8 to 12 cP at 40° C.

When the composition of this invention contains two or more monomers,for example, they can be present in any desirable amounts that wouldbring about the intended benefit, including viscosity modification orimprovement in thermal and mechanical properties or both. Accordingly,the molar ratio of first monomer of formula (I) to second distinctmonomer of formula (I) can be from 1:99 to 99:1. In some embodiments,the molar ratio of first monomer of formula (I):second distinct monomerof formula (I) is in the range from 5:95 to 95:5; in some otherembodiments it is from 10:90 to 90:10; it is from 20:80 to 80:20; it isfrom 30:70 to 70:30; it is from 60:40 to 40:60; and it is 50:50, and soon. Similarly, when more than two different monomers of formula (I) areemployed, any ratios of such monomers can be used that would bring aboutthe intended result.

In general, the compositions in accordance with the present inventionencompass the above described one or more of the monomer of formula (I)and if needed additional monomers of formula (I) distinct from eachother, as it will be seen below, various composition embodiments areselected to provide properties to such embodiments that are appropriateand desirable for the use for which such embodiments are directed, thussuch embodiments are tailorable to a variety of specific applications.

For example, as already discussed above, proper combination ofdistinctive monomers of formula (I) makes it possible to tailor acomposition having the desirable viscosity, thermal and mechanicalproperties. In addition, as described further herein it may be desirableto include other polymeric or monomeric materials as additives, such asfor example inorganic nanoparticles which are compatible to providedesirable optical properties depending upon the end use application.Accordingly, the compositions of this invention can also include otherpolymeric materials and/or nanoparticles which will bring about suchintended benefit. Examples of such polymers include without anylimitation, polystyrene, poly(α-methylstyrene), poly(vinyl-toluene),copolymers of β-methylstyrene and vinyl-toluene, and the like. Otherpolymers that may be suitable as additives in the compositions of thisinvention include elastomeric polymers, including a wide variety ofrubbers, both natural and synthetic rubber. Non-limiting examples ofsynthetic rubbers include polyisobutylene (PIB), polybutadiene,polyisoprene, random and block copolymers of butadiene and/or isoprenewith styrene, styrene-butadiene rubbers (SBR), chloroprene rubbers, andthe like. In some embodiments certain of these polymers and/ornanoparticles also function as viscosity modifiers depending upon thetype of monomers employed. Accordingly, in some embodiments of thisinvention polystyrene is used as viscosity modifier.

The compositions in accordance with the present invention may furthercontain optional additives as may be useful for the purpose of improvingproperties of both the composition and the resulting object madetherefrom. Such optional additives for example may include anti-oxidantsand synergists. Any of the anti-oxidants that would bring about theintended benefit can be used in the compositions of this invention.Non-limiting examples of such antioxidants include pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (IRGANOX™ 1010from BASF), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl esterbenzenepropanoic acid (IRGANOX™ 1076 from BASF) and thiodiethylenebis[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)propionate] (IRGANOX™ 1035from BASF). Non-limiting examples of such synergists include certain ofthe secondary antioxidants which may provide additional benefits such asfor example prevention of autoxidation and thereby degradation of thecomposition of this invention and extending the performance of primaryantioxidants, among other benefits. Examples of such synergists include,tris(2,4-ditert-butylphenyl)phosphite, commercially available as IRGAFOS168 from BASF, among others.

Advantageously, it has further been found that the compositions of thisinvention can also contain additional monomers. In some embodiments, thecomposition according to this invention may further contain one or moresecond monomer selected from the monomer of formula (IV).

In this aspect of the invention, it has now been found that monomer offormula (IV) provides further advantages. Namely, the monomer of formula(IV) depending upon the nature of the monomer may impart highthermo-mechanical properties, thus it can be tailored to meet the need.In addition, the monomer of formula (IV) may exhibit low viscosity andgood solubility for the latent catalyst and/or activator, among variousother advantages.

Again, any amount of monomer of formula (I) with a monomer of formula(IV), if needed, can be employed to form the compositions of thisinvention. Accordingly, the molar ratio of monomer of formula (I) tomonomer of formula (IV) can be from 0:100 to 100:0 or from 1:99 to 99:1.In some embodiments, the molar ratio of monomer of formula (I):monomerof formula (IV) is in the range from 5:95 to 95:5; in some otherembodiments it is from 10:90 to 90:10; it is from 20:80 to 80:20; it isfrom 30:70 to 70:30; it is from 60:40 to 40:60; and it is 50:50, and soon. Similarly, when more than one monomer of formula (I) and more thanone monomer of formula (IV) are employed, any ratios of such monomerscan be used that would bring about the intended result.

In some embodiments the composition according to this inventionencompasses a monomer of formula (I) wherein m is 1 and each of R₁, R₂,R₃ and R₄ are hydrogen. In some other embodiments the compositionaccording to this invention encompasses a monomer of formula (I) whereinm is 0 and at least one of R₁, R₂, R₃ and R₄ is other than hydrogen andis a group as defined above and the remaining R₁, R₂, R₃ and R₄ arehydrogen.

In some embodiments the composition according to this inventionencompasses a monomer of formula (IV) where R₁₈ is hydrogen. In someembodiments the composition according to this invention encompasses amonomer of formula (IV) where R₁₈ is methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, tert-butyl, phenyl, benzyl, phenethyl,methoxy, ethoxy, phenoxy, benzyloxy, acetoxy and benzoyl.

In some embodiments the composition of this invention encompasses firstand second monomer of formula (I) distinct from each other, wherein saidfirst monomer is of formula (I) wherein m is 1 and each of R₁, R₂, R₃and R₄ are hydrogen; and wherein said second monomer is of formula (I)wherein m is 0, R₁ is decyl and each of R₂, R₃ and R₄ are hydrogen.

Accordingly, any of the monomers within the scope of monomer of formula(I) can be employed in the composition of the invention. Representativeexamples of monomer of formula (I) include the following without anylimitations:

-   tetracyclododecene (TD);

-   2-phenyl-tetracyclododecene (PhTD);

-   2-benzyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;

-   2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene    (PETD);

-   2-butyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene    (ButylTD);

-   2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene    (HexylTD);

-   2-octyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene    (OctylTD);

-   2-decyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene    (DecylTD);

-   2-cyclohexyl-tetracyclododecene (CyclohexylTD);

-   2-cyclohexylmethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;

-   2-cyclohexylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;

-   (1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalen-2-yl)methyl    acetate (TDMeOAc);

-   tetracyclododecadiene (TDD);

-   5-(4-phenylbutyl)bicyclo[2.2.1]hept-2-ene;

-   5-(3-phenylpropyl)bicyclo[2.2.1]hept-2-ene;

-   5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);

-   5-benzylbicyclo[2.2.1]hept-2-ene;

-   5-(benzyloxy)bicyclo[2.2.1]hept-2-ene;

-   5-(2-([1,1′-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene;

-   5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene    (NBEtO-2-PhPh);

-   5-butylbicyclo[2.2.1]hept-2-ene (BuNB);

-   5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB);

-   5-octylbicyclo[2.2.1]hept-2-ene (OctNB);

-   5-decylbicyclo[2.2.1]hept-2-ene (DecylNB);

-   5-ethylidenebicyclo[2.2.1]hept-2-ene;

-   2-ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;

-   3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene    (one of trimers of cyclopentadiene, TCPD1, also known as CPD3);

-   5-norbornenylmethyleugenyl acetate (EuAcNB);

-   3-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl acetate (PhAcNB);

-   1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBBuNB); and

-   5-(2-([1,1′-biphenyl]-4-yl)ethyl)bicyclo[2.2.1]hept-2-ene    (NBEtPhPh).

Representative examples of monomer of formula (IV) include the followingwithout any limitations:

-   dicyclopentadiene (DCPD);

-   4,4a,4b,5,8,8a,9,9a-octahydro-1H-1,4:5,8-dimethanofluorene (one of    trimers of cyclopentadiene, TCPD2);

-   1-methoxy-dicyclopentadiene;

-   1-(n-butoxy)-dicyclopentadiene;

-   1-(n-octyloxy)-dicyclopentadiene;

-   3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl acetate;

-   3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl benzoate;

-   3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl 2-phenylacetate; and

-   3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl 3-phenylpropanoate.

In addition, the composition of this invention contains optionally atleast one or more compounds of formulae (VIIa), (VIIb) or (VIIc).Advantageously, it has now been found that incorporating one or morecompounds of formulae (VIIa), (VIIb) or (VIIc) it is possible to tailorthe properties of the compositions for the intended purpose. Forexample, suitable combination of one or more compounds of formulae(VIIa), (VIIb) or (VIIc) with the composition of this invention it isnow possible to improve the mechanical properties of the articles formedfrom the composition of this invention among other properties. Moreparticularly it has now been found that incorporation of certainsiloxane compounds within the scope of compounds of formulae (VIIa) or(VIIb) improves the impact strength of the products formed therefrom.Any amount of one or more compounds of formula (VIIa), (VIIb) or (VIIc)can be employed that would bring about the intended benefit. In generalsuch amounts may range from 0 to 20 mole percent of compounds offormulae (VIIa), (VIIb) and (VIIc) based upon the total moles ofcompounds of formulae (I), (IV), (VIIa), (VIIb) and (VIIc). In someembodiments such amounts may range from 1 to 15 mole percent, and insome other embodiments such amounts may range from 1.5 to 10 molepercent.

Accordingly, in some embodiments the impact strength of the polymersformed from the composition of this invention is at least 40 J/m. Insome other embodiments the impact strength of the polymers formed fromthe composition of this invention is at least 60 J/m. In yet some otherembodiments the impact strength of the polymers formed from thecomposition of this invention is at least 80 J/m, 100 J/m or higher, 140J/m or higher or it can be higher than 160 J/m, such as for examplehigher than 170 J/m, higher than 180 J/m, higher than 200, 220 or 240J/m, or even higher than 500, 550, 600, 700 or 800 J/m depending uponthe types of monomers employed as described herein.

In some embodiments the compounds of formulae (VIIa), (VIIb) or (VIIc)are each having m=0 and K=CH₂. In some embodiments the compounds offormulae (VIIa), (VIIb) or (VIIc) are each having m=1 and K=CH₂. In yetsome other embodiments the compounds of formulae (VIIa), (VIIb) or(VIIc) are each having m=2 and K=CH₂.

Representative examples of compounds within the scope of formulae (VIIa)or (VIIb) without any limitation includes the following:

-   1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane    (BisENBTMDS);

-   1,1,3,3-tetramethyl-1,3-bis(2-(1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalen-2-yl)ethyl)disiloxane;

-   1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane    (BisENBHMTS);

-   1,1,3,3,5,5-hexamethyl-1,5-bis(2-(1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalen-2-yl)ethyl)trisiloxane;

-   1,4-bis((2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)dimethylsilyl)benzene;

-   3,3′-oxybis(1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-3-cyclohexyl-1,1,5,5-tetramethyltrisiloxane)    (TeTENBOMSS);

-   (bicycloheptenyl)ethyl terminated polydimethylsiloxane, where n is 2    to 4; and

-   3,7,14-tris(((2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)dimethylsilyl)oxy)-1,3,5,7,9,11,14-heptaisobutyl-2,4,6,8,10,12,13,15,16-nonaoxa-1,3,5,7,9,11,14-heptasilatricyclo[7.30.3.15,11]hexadecane    (trisnorbornenylisobutyl POSS).

In addition various other oligomeric or polymeric polysiloxanes withmulti-functional cycloolefinic pendent groups are suitable ascrosslinking molecules in the composition of this invention which may ormay not be within the scope of compound of formula (VIIa). Such examplesinclude an oligomeric siloxane of the formula:

Where b is an integer from 1 to 9;n is an integer from 1 to 10; andR_(b) and R_(c) are independently selected from the group consisting ofmethyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl and phenyl.

Various other non-limiting examples of the compounds of formulae (VIIa),(VIIb) or (VIIc) maybe selected from the group consisting of:

-   1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane;

-   5,5′-(oxybis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

-   5,5′-(oxybis(ethane-2,1-diyl))bis(bicyclo[2.2.1]hept-2-ene);

-   bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methane;

-   5,5′-((propane-2,2-diylbis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

-   5,5′-((propane-1,1-diylbis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

-   5,5′-(((1-phenylethane-1,1-diyl)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

-   1,2-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethane;

-   1,3-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)propane;

-   1,4-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)butane;

-   1,6-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)hexane;

-   1,8-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)octane;

-   bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethylsilane;

-   where n is 2 to 4;

-   Where R and R′ are independently selected from (C₁-C₁₂alkyl),    (C₆-C₁₀aryl) and (C₆-C₁₀aryl)(C₁-C₁₂alkyl);

-   bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)(phenyl)silane;

-   bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)diphenylsilane;

-   1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)benzene;

-   1,3-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)benzene;

-   bis(bicyclo[2.2.1]hept-5-en-2-ylmethyl) carbonate;

-   bicyclo[2.2.1]hept-5-en-2-ylmethyl    bicyclo[2.2.1]hept-5-ene-2-carboxylate;

-   Where b is an integer from 1 to 6;

-   bis(bicyclo[2.2.1]hept-5-en-2-ylmethyl) terephthalate;

-   bicyclo[2.2.2]oct-5-en-2-ylmethyl    bicyclo[2.2.2]oct-5-ene-2-carboxylate;

-   5,5′-((((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(2,3,5,6-tetrafluoro-4,1-phenylene))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

-   5,5′-(((((perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(oxy))bis(2,3,5,6-tetrafluoro-4,1-phenylene))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene)

-   1,4,4a,4b,5,8,8a,8b-octahydro-1,4:5,8-dimethanobiphenylene;

-   4,4a,4b,5,8,8a,9,9a-octahydro-1H-1,4:5,8-dimethanofluorene;

-   1,4,4a,5,8,8a,9,9a,10,10a-decahydro-1,4:5,8-dimethanoanthracene;

-   1,4,4a,5,6,6a,7,10,10a,11,12,12a-dodecahydro-1,4:7,10-dimethanodibenzo[a,e][8]annulene;    and

-   1,4,4a,5,5a,5b,6,6a,7,10,10a,11,11a,11b,12,12a-hexadecahydro-1,4:5,12:6,11:7,10-tetramethanodibenzo[b,h]biphenylene.

Various other non-limiting examples within the scope of the compounds offormula (VIIa), (VIIb) and (VIIc) maybe enumerated as follows:

-   1,3-di(bicyclo[2.2.1]hept-5-en-2-yl)propane;

-   5,5′-(2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)propane-1,3-diyl)bis(bicyclo[2.2.1]hept-2-ene);

-   bis(4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane;

-   tris(4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane;

-   5,5′-(((2-((bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl)-2-methylpropane-1,3-diyl)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

-   5,5′-(((bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

-   tris(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)silane; and

-   bicyclo[2.2.1]hept-5-en-2-ylbis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)silane.

In some embodiments the composition of this invention encompasses one ormore monomer of formula (I), which is selected from the group consistingof:

-   tetracyclododecene (TD);-   2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene    (PETD);-   2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene    (HexylTD);-   2-decyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene    (DecylTD);-   3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene    (CPD3);-   5-butylbicyclo[2.2.1]hept-2-ene (BuNB);-   5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB);-   5-decylbicyclo[2.2.1]hept-2-ene (DecylNB);-   5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);-   5-(2-([1,1′-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene; and-   5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene    (NBEtO-2-PhPh).

In some embodiments the composition of this invention further includes amonomer of formula (IV), which is dicyclopentadiene (DCPD). It should benoted that mixtures in any combination of aforementioned monomers offormula (I) and monomers of formula (IV) can be employed in thecompositions of this invention so as to obtain the intended benefit forforming the desirable 3D objects and can be tailored in accordance withthe properties required for the formation of such 3D objects.

In a further embodiment of this invention, the composition contains anyof the latent catalyst that would bring about the mass polymerization asdescribed herein under ROMP conditions. Generally, such suitable latentcatalysts include a number of known organo-transition metal complexes,such as organo-ruthenium or organo-osmium compounds, among others. Forexample, U.S. Pat. No. 9,328,132 B2, pertinent portions of which areincorporated herein, discloses a series of organo-ruthenium compounds,which are pre-catalysts for the olefin metathesis reactions, all of suchcatalysts may be suitable as latent catalysts in the compositions ofthis invention.

Accordingly, the composition of this invention encompasses a latentcatalyst which is an organo-ruthenium compound selected from the groupconsisting of compounds of formulae (IIA), (IIB), (IIIA), (IIIB) and(IIIC):

and

-   -   wherein:    -   X is a halogen or an anionic ligand;    -   Y is selected from the group consisting of O and S;    -   Y′ is OR₉ SR₉ and —N═CHC(O)O(C₁-C₆)alkyl, where R₉ is selected        from the group consisting of methyl, ethyl, linear or branched        (C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linear or branched        (C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy, —OCH(CH₃)C(O)N(CH₃)(OCH₃);    -   L is PR₃ or O═PR₃, where R is independently selected from the        group consisting of isopropyl, sec-butyl, tert-butyl,        cyclohexyl, bicyclo(C₅-C₁₀)alkyl, phenyl, benzyl, isopropoxy,        sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy;        or    -   X and L form a bidentate anionic ligand of the formula X-L;    -   R₇ is selected from the group consisting of isopropyl,        sec-butyl, tert-butyl, substituted or unsubstituted cyclohexyl,        substituted or unsubstituted phenyl, substituted or        unsubstituted biphenyl and substituted or unsubstituted        naphthyl;    -   R₈ is selected from the group consisting of methyl, ethyl,        linear or branched (C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy,        linear or branched (C₁-C₆)alkoxy, (C₆-C₁₀) aryloxy,        —NHCO(C₁-C₆)alkyl, —NHCO-perfluoro(C₁-C₆)alkyl,        —SO₂N((C₁-C₆)alkyl)₂ and —NO₂;    -   Ar₁, Ar₂ Ar₃ and Ar₄ are the same or different and each        independently selected from the group consisting of substituted        or unsubstituted phenyl, substituted or unsubstituted biphenyl        and substituted or unsubstituted naphthyl;

wherein said substituents are selected from the group consisting ofmethyl, ethyl, iso-propyl, tert-butyl and phenyl.

It should be noted that in the above formulae (IIA), (IIB), (IIIA),(IIIB) and (IIIC), X can include any of the halogens. In someembodiments X is chlorine, bromine and iodine.

Generally, any of the latent organo-transition metal catalyst that wouldbring about ring open metathesis polymerization of the monomers offormula (I) and monomers of formula (IV), if present, can be employed inthe composition of this invention. More specifically, organo-rutheniumor organo-osmium compounds that show little or no activity at ambienttemperatures can be employed. That is, the latent catalysts that arestable at or near room temperature are more suitable in the compositionof this invention. The latent catalysts may be activated by a variety ofconditions, including without any limitation acid and chemicalactivation. The chemical activation may include use of thermal acidgenerators or photo acid generators.

Several of the latent catalysts that are suitable to be employed in thecompositions of this invention are known in the literature or can bereadily made by any of the known procedures in the art. See for example,Grubbs, et al., Organometallics, 2011, 30 (24): 6713-6717; Sutar et al.,Angew. Chem. Int. Ed. 2016, 55, 764-767; Leitgeh, et al., Monatsh Chem(2014) 145:1513-1517; van Hensbergen, et al., J. Mater. Chem. C. 2015,3, 693-702; Grubbs, et al., J. Am. Chem. Soc., 2009, 131, 203802039;Zak, et al., Eur. J. Inorg. Chem., 2014, 1131-1136; Gawin, et al., ACSCatal. 2017, 7, 5443-5449. As noted above, further examples of suchcatalysts can also be found in U.S. Pat. No. 9,328,132. Accordingly, afew of the exemplary latent catalysts, which are organo-rutheniumcompounds, without any limitation maybe selected from the groupconsisting of:

-   1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)    chloride;

-   where X=halogen, —OR_(a), —O(CO)R_(a) —OSO₂R_(a), where R_(a) is    (C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₄)aryl;

-   where X is Cl or I and R₁₀ is hydrogen, NO₂ or Cl;

-   cis-[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)(triisopropylphosphite)ruthenium(II);    and

-   1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium.

As noted, the composition of this invention further contains a compoundcapable of releasing a Bronsted acid when subjected to suitablephotolytic conditions. The anion, for example chloride, of so releasedBronsted acid activates the latent catalyst. Surprisingly it has nowbeen found that certain of the known photoactive compounds, such as forexample, a class of substituted xanthone derivatives can be used forthis purpose.

Accordingly, in some embodiments such xanthone derivatives are of theformula (V):

Wherein Y is halogen; and R₃₀ and R₃₁ are the same or different andindependently of each other selected from hydrogen, methyl, ethyl,linear or branched (C₃-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₃-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)-aryloxy. In some embodiments Yis fluorine, chlorine, bromine and iodine. In some embodiments Y ischlorine. In some other embodiments R₃₀ is hydrogen and R₃₁ is selectedfrom the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy,butoxy, and the like.

Further, it has also been found that a variety of substituted triazinesof the formula (VI) are also suitable as a compound capable of releasinga Bronsted acid when subjected to suitable photolytic conditions.

wherein

R₃₂, R₃₃ and R₃₄ are the same or different and independently of eachother selected from the group consisting of halogen, methyl, ethyl,linear or branched (C₃-C₁₂)alkyl, trihalomethyl, pentahaloethyl, linearor branched perhalo(C₃-C₁₂)alkyl, (C₆-C₁₀) aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, perhalo (C₆-C₁₀) aryl, perhalo (C₆-C₁₀)arylperhalo(C₁-C₃)alkyl, substituted or unsubstituted five membered or six memberedheteroaryl(C₂-C₄)alkenyl and substituted or unsubstituted(C₆-C₁₀)aryl(C₂-C₄)alkenyl provided that one of R₃₂, R₃₃ and R₃₄ istrihalomethyl, pentahaloethyl, linear or branched perhalo(C₃-C₁₂)alkyl.

Representative examples of the compounds of formula (V) may be listed asfollows:

-   1-chloro-4-methoxy-9H-thioxanthen-9-one;

-   1-chloro-4-ethoxy-9H-thioxanthen-9-one;

-   1-chloro-4-propoxy-9H-thioxanthen-9-one (commercially sold under the    name CPTX from Lambson);

-   1-chloro-2-propoxy-9H-thioxanthen-9-one;

-   1-chloro-2-ethoxy-9H-thioxanthen-9-one;

-   1-chloro-2-methoxy-9H-thioxanthen-9-one;

-   1-chloro-4-methyl-9H-thioxanthen-9-one;

-   1-chloro-4-ethyl-9H-thioxanthen-9-one;

-   1-bromo-4-propoxy-9H-thioxanthen-9-one; and

-   1-chloro-4-phenoxy-9H-thioxanthen-9-one.-   Representative examples of the compounds of formula (VI) without any    limitation may be enumerated as follows:

-   2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine;

-   2-ethyl-4,6-bis(trichloromethyl)-1,3,5-triazine;

-   2-methyl-4,6-bis(tribromomethyl)-1,3,5-triazine;

-   2-(2-(furan-2-yl)vinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine;

-   2-(2-(thiophen-2-yl)vinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine;

-   2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine; and

-   2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

Advantageously, it has now been found that any of the compounds offormula (V) or compounds of formula (VI) which generates a Bronsted acidwhen subjected to photolytic conditions can be used in the compositionsof this invention. The generated Bronsted acid will activate the latentcatalysts of formulae (IIA), (IIB), (IIIA), (IIIB) or (IIIC) therebyinitiating the ROMP of monomers of formula (I), one or more compounds offormulae (VIIa), (VIIb) or (VIIc), and monomers of formula (IV), ifpresent, thus causing the compositions of this invention to form 3Dobjects. Generally, any of the Bronsted acids can cause such activationof catalyst. Non-limiting examples of such Bronsted acids includewithout any limitation hydrofluoric acid, hydrochloric acid, hydrobromicacid, hydroiodic acid, trifluoroacetic acid, trifluoromethanesulfonicacid, and the like. In some embodiments the Bronsted acid generated ishydrochloric acid.

In some embodiments the compounds of formula (V) can be activated atcertain wavelength of the electromagnetic radiation which can generallyrange from about 240 nm to 400 nm. Accordingly, any of the compoundswhich are active in this electromagnetic radiation can be employed inthe compositions of this invention which are stable to the 3Dfabrication methods. In some embodiments the wavelength of the radiationto activate the compounds of formula (V) is 260 nm. In some otherembodiments the wavelength of the radiation to activate the compounds offormula (V) is 310 nm. In yet some other embodiments the wavelength ofthe radiation to activate the compounds of formula (V) is 395 nm.

However, any of the other known photoactive compounds which generate theBronsted acid in order to activate the latent catalysts employed hereincan also be used in the composition of this invention. All suchcompounds are part of this invention.

In some embodiments of this invention the composition of this inventionmay additionally contain other photosensitizer compounds which canactivate the organo-transition compound in order to facilitate the masspolymerization of the monomers of formula (I), one or more compounds offormulae (VIIa), (VIIb) or (VIIc) and monomers of formula (IV), ifpresent. For this purpose, any suitable sensitizer compound can beemployed in the compositions of the present invention. Such suitablesensitizer compounds include, photosensitizers, such as, anthracenes,phenanthrenes, chrysenes, benzpyrenes, fluoranthenes, rubrenes, pyrenes,xanthones, indanthrenes, and mixtures thereof. In some exemplaryembodiments, suitable sensitizer components include mixtures thereof.Generally, the photosensitizers absorb energy from the radiated lightsource and transfers that energy to the desirable substrate/reactant,which in the present invention is the compound of formula (V) employedin the composition of this invention.

Any amount of latent catalyst and the compound of formula (V) can beemployed in the composition of this invention which will bring about theintended result. Generally, the molar ratio of monomer:latentcatalyst:compound of formula (V) or a compound of formula (VI) is in therange of 10,000:1:1 to 5,000:1:1 or lower. In some other embodiments,the compound of formula (V) is employed at higher level than the latentcatalyst, for example, such ranges may include monomer:latentcatalyst:compound of formula (V) or a compound of formula (VI) is10,000:1:2, 10,000:1:4 or higher. In some other embodiments suchmonomer:latent catalyst: compound of formula (V) or a compound offormula (VI) is 15,000:1:4, 20,000:1:4 or higher.

Advantageously, it has further been found that the composition accordingto this invention forms a substantially three dimensional object whenmass polymerized, generally, when exposed to suitable radiation at awavelength in the range from 260 nm to 400 nm. That is to say, when thecomposition of this invention is exposed to suitable radiation, themonomers undergo mass polymerization to form solid objects under routine3D printing technologies.

In some embodiments the composition of this invention undergoes masspolymerization when exposed to suitable UV irradiation which issubstantially free of any monomer or volatile oligomeric product.

It has also been found that various other viscosity modifiers that arecompatible with the compositions of this invention can also be employedin order to modulate the viscosity of the composition before subjectingit to the mass polymerization conditions. Suitable examples of suchviscosity modifiers include transparent polymers such as for examplepolystyrene, polyesters (polyethylene terphthalate, PET), and the like.

Accordingly, in some embodiments of this invention there is provided acomposition comprising one or more monomers of formula (I), one or morecompounds of formulae (VIIa), (VIIb) or (VIIc), optionally one or moremonomers of formula (IV), a latent catalyst, a compound of formula (V)as described hereinabove. Any of the monomers of formula (I) asdescribed hereinabove can be used in this aspect of the invention alongwith one or more compounds of formulae (VIIa), (VIIb) or (VIIc),optionally in combination with one or more monomers of formula (IV). Themonomers of formula (I) featuring a viscosity below 50 centipoise aregenerally employed. When more than two monomers of formula (I) areemployed the first monomer is completely miscible with the secondmonomer and forms a clear solution. Further, combining such solutionwith one or more compounds of formulae (VIIa), (VIIb) or (VIIc) providesa clear solution. When the composition is exposed to suitableirradiation and fabricated under suitable 3D printing conditions forms a3D object.

In another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD),1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane(BisENBTMDS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD),1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane(BisENBHMTS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD), 5-decylbicyclo[2.2.1]hept-2-ene (DecylNB),1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane(BisENBTMDS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD), trisnorbornenylisobutyl POSS,1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD),3,3′-oxybis(1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-3-cyclohexyl-1,1,5,5-tetramethyltrisiloxane(TeTENBOMSS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD),3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene(CPD3);3,3′-oxybis(1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-3-cyclohexyl-1,1,5,5-tetramethyltrisiloxane(TeTENBOMSS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD),3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene(CPD3); 5-decylbicyclo[2.2.1]hept-2-ene (DecylNB),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD),3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene(CPD3);1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-decyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(DecylTD),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In a further aspect of this invention there is also provided a kit forforming a three dimensional object. There is dispensed in this kit acomposition of this invention. Accordingly, in some embodiments there isprovided a kit in which there is dispensed one or more monomers offormula (I), optionally one or more compounds of formulae (VIIa), (VIIb)or (VIIc), optionally one or more monomers of formula (IV) and acompound of formula (V), so as to obtain a desirable result and/or forintended purpose. Further, said kit comprises a latent catalyst asdescribed herein. The monomers of formulae (I), monomers of formula(IV), and compounds of formulae (VIIa), (VIIb) or (VIIc) are the ones asdescribed hereinabove. Any of the monomers of formula (I) in combinationwith any of the monomers of formula (IV), if needed, and any of thecompounds of formulae (VIIa), (VIIb) or (VIIc), if needed, can bedispensed in the kit with desirable respective quantities so as toobtain the intended result.

In some embodiments, the aforementioned kit encompasses two or moremonomers of formula (I) distinct from one another as describedhereinabove. In some other embodiments the kit of this inventionencompasses at least two monomers wherein first monomer facilitatesdissolution of the second monomer and/or the latent catalyst and theadditives as described hereinabove. Any of the monomers of formula (I)as described herein can be used in this embodiment. The molar ratio offirst and the second monomer of formula (I) contained in thesecomponents can vary and may range from 1:99 to 99:1, or 10:90 to 90:10,20:80 to 80:20, 30:70 to 70:30, 60:40 to 40:60 or 50:50, and so on. Insome other embodiments the kit may encompass a composition whereindispensed more than two monomers of formula (I), each distinct from oneanother. Further, as noted the first monomer of formula (I) iscompletely soluble in the second monomer of formula (I) to form a clearsolution at room temperature. In some embodiments the monomer mixturemay become a clear solution at slightly elevated temperature, such asfor example, 30° C. or 40° C. or 50° C. or 70° C. or higher, before theyundergo mass polymerization. In another aspect of this embodiment ofthis invention the composition of this invention undergoes masspolymerization when exposed to a suitable radiation for a sufficientlength of time to form a 3D object. That is to say that the compositionof this invention when used in a suitable 3D printing system capable ofexposing to a suitable radiation forms a desirable 3D object. Generally,as already noted above, such polymerization can take place when exposedto suitable radiation at a wavelength from about 260 nm to 400 nm orhigher. The exposure can be at stages from 260 nm to 400 nm or atsuitable wavelengths as described herein. By practice of this inventionit is now possible to form 3D objects using any of the known 3D printingtechnologies.

In some embodiments the kit according to this invention contains atleast two monomers of formula (I) distinct from one another, wherein onemonomer is completely soluble in the other monomer, and when saidcomposition is exposed to radiation at 395 nm for a sufficient length oftime it forms a three dimensional object.

In some embodiments, the kit as described herein encompasses acomposition, which contains a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD),1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane(BisENBTMDS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In some embodiments, the kit as described herein encompasses acomposition, which contains a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD),1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane(BisENBHMTS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

In some embodiments, the kit as described herein encompasses acomposition, which contains a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD), 5-decylbicyclo[2.2.1]hept-2-ene (DecylNB),1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane(BisENBTMDS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

As noted, the compositions of this invention can be used in any of theknown three dimensional (3D) printing technologies and other printingtechnologies. A few of the 3D printing procedures known in the artinclude continuous liquid interface production (CLIP), layer by layerapproach (LBL), inkjet printing and frontal polymerization method, suchas frontal ring open metathesis (FROMP) technique, see for exampleRobertson et al., Nature, Vol. 557, 223-227 (2018).

In a CLIP approach, a 3D object is continuously formed by projecting acontinuous sequence of UV images (generated by a digitallight-processing (DLP) imaging unit or a laser to generate the part)through an oxygen permeable, UV-transparent window below a liquid resinbath containing the compositions of this invention. The dead zonecreated above the window maintains a liquid interface below theadvancing part. Above the dead zone, the curing part is continuouslydrawn out of the resin bath. The suction forces resulted due to thisdrawing replenishes the resin bath at the same time. In this way variousparts of different dimensions up to several centimeters with partresolution lower than 100 microns can be fabricated.

In a 3D inkjet printing technology, the compositions of this inventioncan be used as photopolymerizable ink compositions to form lines andvias on a substrate, typically on a silicon wafer. A wide variety ofparts having utility in electronic and optoelectronic applications canthus be manufactured using the compositions of this invention. Nonlimiting examples of such applications include manufacturing of OLEDdevices on a variety of substrates, which can be produced substantiallyin a particle free environment at high yields. The compositions of thisinvention may act as organic encapsulant layers and/or as fillermaterials in some of such OLED devices.

Accordingly, in yet another aspect of this invention there is furtherprovided a method of forming a three dimensional object comprising:

providing a homogeneous clear composition in a suitable container, thecomposition comprising one or more monomers of formula (I), one or morecompounds of formulae (VIIa), (VIIb) or (VIIc), a latent catalyst and acompound of formula (V) or a compound of formula (VI), optionally incombination with one or more monomers of formula (IV);

exposing to suitable UV radiation while drawing the composition from thecontainer; and

forming a three dimensional object.

The 3D objects formed in accordance with the method of this inventionexhibit excellent thermal and mechanical properties. In general, theproperties of these objects can be tailored to intended end use. Forexample, the thermal properties of the 3D objects can be tailored to bestable up to 180° C. or higher depending upon the types of monomers offormula (I) in combination with monomers of formula (IV) employed toform such 3D objects. Similarly, the mechanical properties can also betailored to desired mechanical properties simply by the selection ofsuitable monomers as described herein. In general, by tailoring theproper choice of monomers the parts possessing very high impact strengthcan be fabricated.

Accordingly, in some of the embodiments of this invention there is alsoprovided a three dimensional object comprising the composition of thisinvention which exhibits excellent thermal and mechanical properties.

The following examples are detailed descriptions of methods ofpreparation and use of certain compounds/monomers, polymers andcompositions of the present invention. The detailed preparations fallwithin the scope of, and serve to exemplify, the more generallydescribed methods of preparation set forth above. The examples arepresented for illustrative purposes only, and are not intended as arestriction on the scope of the invention. As used in the examples andthroughout the specification the ratio of monomer to catalyst is basedon a mole to mole basis.

EXAMPLES

The following abbreviations have been used hereinbefore and hereafter indescribing some of the compounds, instruments and/or methods employed toillustrate certain of the embodiments of this invention:PETD—2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;DecylNB—5-decylbicyclo[2.2.1]hept-2-ene;BisENBTMDS—1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane;BisENBHMTS—1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane;TeTENBOMSS—3,3′-oxybis(1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-3-cyclohexyl-1,1,5,5-tetramethyltrisiloxane;CPD3—3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene;HexylTD—2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;DecylTD—2-decyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;Ru-II—1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium;CPTX—1-chloro-4-propoxy-9H-thioxanthen-9-one; DSC—differential scanningcalorimetry; TGA—thermogravimetric analysis.

Various monomers as used herein are either commercially available or canbe readily prepared following the procedures as described in U.S. Pat.No. 9,944,818.

The following Examples demonstrate that the compositions of thisinvention are quite stable at ambient temperature conditions and even upto 35° C. for several days and can very readily be mass polymerized byexposing to a suitable radiation as specified below.

Example 1 Mass Polymerization of PETD/BisENBTMDS

In a glass bottle, Ru-II (1 molar part) and CPTX (8 molar parts) weredissolved in PETD (9,500 molar parts) and BisENBTMDS (500 molar parts)without solvent to form a clear solution. The solution was heated to 70°C. and UV light exposed for 4 seconds (LED 270 mW/cm², 395 nm). Thesolution turned to a solid indicating the monomer was fully polymerized,as confirmed by both DSC and TGA. The residue percentage from isothermalTGA (1 h at 100° C.) after UV exposure was >99%. The unexposed solutionwas free flowing even after 21 days at room temperature. This indicatesthat during the UV exposure CPTX releases a chloride ion that activatesRu-II catalyst. A sample was prepared for impact strength measurement inaccordance with ASTM D256 and the impact strength was 160 J/m.

Examples 2-22 Mass Polymerization of Various Monomers

The procedures of Example 1 were substantially repeated in theseExamples 2 to 22 except that various monomers and at different molarratios as listed in Table 1 were employed. The monomers used and theirmolar ratios along with the measured impact strength of the resultingpolymers are summarized in Table 1.

TABLE 1 Example Monomers Impact No. (molar parts) Strength (J/m) 2PETD/BisENBTMDS 106 90/10 molar ratio 3 PETD/BisENBHMTS 186 95/5 molarratio 4 PETD/BisENBHMTS 104 90/10 molar ratio 5 PETD/DecylNB/BisENBTMDS139 85.5/9.5/5 mole ratio 6 PETD/DecylNB/BisENBTMDS 47 90/9/1 mole ratio7 PETD/trisnorbornenylisobutyl POSS 91 98.5/1.5 mole ratio 8PETD/trisnorbornenylisobutyl POSS 144 97/3 mole ratio 9 PETD/TeTENBOMSS170 98/2 mole ratio 10 PETD/CPD3/TeTENBOMSS 120 95/1/4 mole ratio 11PETD/CPD3/BisENBTMDS 177 94/1/5 mole ratio 12 PETD/CPD3/BisENBTMDS 15590/5/5 mole ratio 13 DecylNB/CPD3/PETD 240 50/25/25 mole ratio 14DecylNB/CPD3/PETD 565 50/10/40 mole ratio 15 HexylTD 786 16 HexylTD/CPD3771 99/1 mole ratio 17 HexylTD/CPD3 736 95/5 mole ratio 18 HexylTD/CPD3603 90/10 mole ratio 19 HexylTD/CPD3 622 85/15 mole ratio 20HexylTD/CPD3 473 80/20 mole ratio 21 DecylTD 578 22HexylTD/CPD3/BisENBTMDS 180 85/10/5 mole ratio

Comparative Example 1

The procedures of Example 6 were substantially repeated in thisComparative Example 1 except that no BisENBTMDS was employed,PETD/DecylNB (90/10 molar ratio). The measured impact strength of theresulting polymer was 29 J/m.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A composition comprising: a) one or more monomersof formula (I):

wherein: m is an integer 0, 1 or 2;

is a single bond or a double bond; R₁, R₂, R₃ and R₄ are the same ordifferent and each independently selected from the group consisting ofhydrogen, halogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,(C₂-C₁₆)alkenyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, methoxy, ethoxy, linear orbranched (C₃-C₁₆)alkoxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, (C₆-C₁₄)aryl,(C₆-C₁₄)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₄)aryl,perfluoro(C₆-C₁₄)aryl(C₁-C₃)alkyl, (C₆-C₁₄)aryloxy,(C₆-C₁₄)aryl(C₁-C₆)alkoxy, tri(C₁-C₆)alkoxysilyl and a group of formula(A):—Z-Aryl  (A) wherein: Z is a bond or a group selected from the groupconsisting of: (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,(CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),(CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which may bethe same or different and each independently is 1 to 12; R₅ and R₆ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl, ethyl, linear or branched (C₃-C₆)alkyl,methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, (C₂-C₆)acyl,(C₂-C₆)acyloxy, phenyl and phenoxy; Aryl is phenyl or phenyl substitutedwith one or more of groups selected from the group consisting of methyl,ethyl, linear or branched (C₃-C₆)alkyl, hydroxy, methoxy, ethoxy, linearor branched (C₃-C₆)alkyloxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, phenyl andphenoxy; or one of R₁ or R₂ taken together with one of R₃ or R₄ and thecarbon atoms to which they are attached to form a (C₅-C₇)carbocyclicring optionally containing one or more double bonds; b) optionally oneor more monomers of formula (IV):

wherein R₁₆ and R₁₇ are the same or different and each independentlyselected from the group consisting of hydrogen, methyl, ethyl, linear orbranched (C₃-C₆)alkyl, methoxy, ethoxy, linear or branched(C₃-C₆)alkyloxy, acetoxy, (C₂-C₆)acyl, phenyl and phenoxy; or R₁₆ takentogether with R₁₇ and the carbon atoms to which they are attached toform a (C₅-C₇)carbocyclic ring optionally containing one or more doublebonds; R₁₈ is hydrogen, halogen, methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, hydroxy, methoxy,ethoxy, linear or branched (C₃-C₁₆)alkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, —O(CO)R₁₉ and —O(CO)OR₁₉, where R₁₉ ismethyl, ethyl, linear or branched (C₃-C₁₆)alkyl, (C₆-C₁₀)aryl and(C₆-C₁₀)aryl(C₁-C₆)alkyl; c) one or more compounds selected from thegroup consisting of: i) a compound of formula (VIIa):

ii) a compound of formula (VIIb):

 and iii) a compound of formula (VIIc):

where m is an integer 0, 1 or 2; b is an integer from 1 to 10; K isselected from the group consisting of CH₂, CH₂—CH₂, O and S; X isselected from the group consisting of O, S, NR_(a), SiR_(b)R_(c),SiR_(b)R_(c)O(SiR_(b)R_(c)O)_(n)SiR_(b)R_(c),SiR_(b)R_(c)(C₆-C₁₀)arylSiR_(b)R_(c), —C(O)—, —C(O)O—, —OC(O)—,—OC(O)—O—, —S—C(O)—, —C(O)—S—, —CH═CH— and —C≡C—; R_(a), R_(b) and R_(c)are independently of each other selected from the group consisting ofhydrogen, methyl, ethyl or a linear or branched (C₃-C₁₂)alkyl,(C₃-C₈)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₆-C₁₂)bicycloalkenyl and(C₆-C₁₂)bicycloalkenyl(C₁-C₃)alkylSi(CH₃)₂, and such that O, NR_(a)and/or S atoms are not linked directly to one another; and n is aninteger from 0 to 10; d) an organo-ruthenium compound selected from thegroup consisting of: a compound of formula (IIB):

a compound of formula (IIIA):

a compound of formula (IIIB):

a compound of formula (IIIC):

1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium;wherein: X is a halogen or an anionic ligand; Y is selected from thegroup consisting of O and S; Y′ is OR₉ SR₉ and —N═CHC(O)O(C₁-C₆)alkyl,where R₉ is selected from the group consisting of methyl, ethyl, linearor branched (C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linear orbranched (C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy, —OCH(CH₃)C(O)N(CH₃)(OCH₃); L isPR₃ or O═PR₃, where R is independently selected from the groupconsisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl,bicyclo(C₅-C₁₀)alkyl, phenyl, benzyl, isopropoxy, sec-butoxy,tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy; or X and L form abidentate anionic ligand of the formula X-L; R₇ is selected from thegroup consisting of isopropyl, sec-butyl, tert-butyl, substituted orunsubstituted cyclohexyl, substituted or unsubstituted phenyl,substituted or unsubstituted biphenyl and substituted or unsubstitutednaphthyl; R₈ is selected from the group consisting of methyl, ethyl,linear or branched (C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linearor branched (C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy, —NHCO(C₁-C₆)alkyl,—NHCO-perfluoro(C₁-C₆)alkyl, —SO₂N((C₁-C₆)alkyl)₂ and —NO₂; Ar₁, Ar₂ Ar₃and Ar₄ are the same or different and each independently selected fromthe group consisting of substituted or unsubstituted phenyl, substitutedor unsubstituted biphenyl and substituted or unsubstituted naphthyl;wherein said substituents are selected from the group consisting ofmethyl, ethyl, iso-propyl, tert-butyl and phenyl; and e) a compoundcapable of releasing a Bronsted acid when subjected to photolyticconditions, said compound selected from the group consisting of: acompound of the formula (V):

wherein Y is halogen; and R₃₀ and R₃₁ are the same or different andindependently of each other selected from the group consisting ofhydrogen, methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)-aryloxy; and a compound of theformula (VI):

wherein R₃₂, R₃₃ and R₃₄ are the same or different and independently ofeach other selected from the group consisting of halogen, methyl, ethyl,linear or branched (C₃-C₁₂)alkyl, trihalomethyl, pentahaloethyl, linearor branched perhalo(C₃-C₁₂)alkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₃)alkyl, perhalo(C₆-C₁₀)aryl,perhalo(C₆-C₁₀)arylperhalo(C₁-C₃)alkyl, substituted or unsubstitutedfive membered or six membered heteroaryl(C₂-C₄)alkenyl and substitutedor unsubstituted (C₆-C₁₀)aryl(C₂-C₄)alkenyl provided that one of R₃₂,R₃₃ and R₃₄ is trihalomethyl, pentahaloethyl, linear or branchedperhalo(C₃-C₁₂)alkyl; and wherein said composition is in a clear liquidform at room temperature.
 2. The composition according to claim 1,wherein said composition comprising first and second monomer of formula(I) distinct from each other and one of said first and second monomershaving a viscosity below 50 centipoise, and wherein said first monomeris completely miscible with said second monomer to form a clearsolution.
 3. The composition according to claim 1, wherein saidcomposition comprising a monomer of formula (I) wherein m is 1 and eachof R₁, R₂, R₃ and R₄ are hydrogen.
 4. The composition according to claim3, wherein said composition comprising a monomer of formula (IV) whereR₁₈ is hydrogen.
 5. The composition according to claim 1, wherein saidone or more compounds of formulae (VIIa), (VIIb) or (VIIc) is selectedfrom the group consisting of:

1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane(BisENBTMDS);

1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane(BisENBHMTS);

1,4-bis((2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)dimethylsilyl)benzene;

3,3′-oxybis(1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-3-cyclohexyl-1,1,5,5-tetramethyltrisiloxane)(TeTENBOMSS);

(bicycloheptenyl)ethyl terminated polydimethylsiloxane, where n is 2 to4; and

3,7,14-tris(((2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)dimethylsilyl)oxy)-1,3,5,7,9,11,14-heptaisobutyl-2,4,6,8,10,12,13,15,16-nonaoxa-1,3,5,7,9,11,14-heptasilatricyclo[7.3.3.15,11]hexadecane(trisnorbornenylisobutyl POSS).
 6. The composition according to claim 1,wherein the monomer of formula (I) is selected from the group consistingof:

tetracyclododecene;

2-phenyl-tetracyclododecene (PhTD);

2-benzyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;

2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD);

2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD);

2-decyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(DecylTD);

(1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalen-2-yl)methylacetate (TDMeOAc);

tetracyclododecadiene;

5-(4-phenylbutyl)bicyclo[2.2.1]hept-2-ene;

5-(3-phenylpropyl)bicyclo[2.2.1]hept-2-ene;

5-phenethylbicyclo[2.2.1]hept-2-ene;

5-benzylbicyclo[2.2.1]hept-2-ene;

5-(benzyloxy)bicyclo[2.2.1]hept-2-ene;

5-(2-([1,1′-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene;

5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene;

5-butylbicyclo[2.2.1]hept-2-ene;

5-hexylbicyclo[2.2.1]hept-2-ene;

5-octylbicyclo[2.2.1]hept-2-ene;

5-decylbicyclo[2.2.1]hept-2-ene;

5-ethylidenebicyclo[2.2.1]hept-2-ene;

2-ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;

3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene;

5-norbornenylmethyleugenyl acetate;

3-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl acetate;

1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBBuNB); and

5-(2-([1,1′-biphenyl]-4-yl)ethyl)bicyclo[2.2.1]hept-2-ene.
 7. Thecomposition according to claim 1 comprising one or more monomers offormula (IV), which is selected from the group consisting of:

dicyclopentadiene;

4,4a,4b,5,8,8a,9,9a-octahydro-1H-1,4:5,8-dimethanofluorene;

1-methoxy-dicyclopentadiene;

1-(n-butoxy)-dicyclopentadiene;

1-(n-octyloxy)-dicyclopentadiene;

3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl acetate;

3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl benzoate;

3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl 2-phenylacetate; and

3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl 3-phenylpropanoate.
 8. Thecomposition according to claim 1, wherein said one or more monomer offormula (I) is selected from the group consisting of: tetracyclododecene(TD);2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD); 5-butylbicyclo[2.2.1]hept-2-ene (BuNB);5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB);5-decylbicyclo[2.2.1]hept-2-ene (DecylNB);5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);5-(2-([1,1′-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene; and5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtO-2-PhPh); and wherein said monomer of formula (IV) isdicyclopentadiene (DCPD); and mixtures in any combination thereof. 9.The composition according to claim 1, wherein the organo-rutheniumcompound is selected from the group consisting of a compound of formula(IIIA), a compound of formula (IIIB) and a compound of formula (IIIC):

and wherein: X is a halogen or an anionic ligand; Y is selected from thegroup consisting of O and S; Y′ is OR₉ SR₉ and —N═CHC(O)O(C₁-C₆)alkyl,where R₉ is selected from the group consisting of methyl, ethyl, linearor branched (C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linear orbranched (C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy, —OCH(CH₃)C(O)N(CH₃)(OCH₃); L isPR₃ or O═PR₃, where R is independently selected from the groupconsisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl,bicyclo(C₅-C₁₀)alkyl, phenyl, benzyl, isopropoxy, sec-butoxy,tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy; or X and L form abidentate anionic ligand of the formula X-L; R₇ is selected from thegroup consisting of isopropyl, sec-butyl, tert-butyl, substituted orunsubstituted cyclohexyl, substituted or unsubstituted phenyl,substituted or unsubstituted biphenyl and substituted or unsubstitutednaphthyl; R₈ is selected from the group consisting of methyl, ethyl,linear or branched (C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linearor branched (C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy, —NHCO(C₁-C₆)alkyl,—NHCO-perfluoro(C₁-C₆)alkyl, —SO₂N((C₁-C₆)alkyl)₂ and —NO₂; Ar₁, Ar₂ Ar₃and Ar₄ are the same or different and each independently selected fromthe group consisting of substituted or unsubstituted phenyl, substitutedor unsubstituted biphenyl and substituted or unsubstituted naphthyl;wherein said substituents are selected from the group consisting ofmethyl, ethyl, iso-propyl, tert-butyl and phenyl.
 10. The compositionaccording to claim 1, wherein the organo-ruthenium compound is selectedfrom the group consisting of:

1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)chloride;

where X=halogen, —OR_(a), —O(CO)R_(a) —OSO₂R_(a), where R_(a) is(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₄)aryl;

where X is Cl or I and R₁₀ is hydrogen, NO₂ or Cl;

cis-[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)(triisopropylphosphite)ruthenium(II);and

1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium.11. The composition according to claim 1, wherein the compound capableof generating Bronsted acid upon subjecting to photolytic condition is acompound of the formula (V), wherein Y is fluorine, chlorine, bromineand iodine; and R₃₀ and R₃₁ are the same or different and independentlyof each other is selected from the group consisting of hydrogen,methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy.
 12. The compositionaccording to claim 11, wherein the compound capable of generatingBronsted acid upon subjecting to photolytic condition is selected fromthe group consisting of:

1-chloro-4-methoxy-9H-thioxanthen-9-one;

1-chloro-4-ethoxy-9H-thioxanthen-9-one;

1-chloro-4-propoxy-9H-thioxanthen-9-one;

1-chloro-2-propoxy-9H-thioxanthen-9-one;

1-chloro-2-ethoxy-9H-thioxanthen-9-one;

1-chloro-2-methoxy-9H-thioxanthen-9-one;

1-chloro-4-methyl-9H-thioxanthen-9-one;

1-chloro-4-ethyl-9H-thioxanthen-9-one;

1-bromo-4-propoxy-9H-thioxanthen-9-one;

1-chloro-4-phenoxy-9H-thioxanthen-9-one;

2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine;

2-ethyl-4,6-bis(trichloromethyl)-1,3,5-triazine;

2-methyl-4,6-bis(tribromomethyl)-1,3,5-triazine;

2-(2-(furan-2-yl)vinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine;

2-(2-(thiophen-2-yl)vinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine;

2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine; and

2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine.
 13. Thecomposition according to claim 1, which is selected from the groupconsisting of: a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD),1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane(BisENBTMDS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX); a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD), 5-decylbicyclo[2.2.1]hept-2-ene (DecylNB),1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane(BisENBTMDS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX); and a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD),1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane(BisENBHMTS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).
 14. A kit forforming a three dimensional object comprising: a) one or more monomersof formula (I):

wherein: m is an integer 0, 1 or 2;

is a single bond or a double bond; R₁, R₂, R₃ and R₄ are the same ordifferent and each independently selected from the group consisting ofhydrogen, halogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,(C₂-C₁₆)alkenyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, methoxy, ethoxy, linear orbranched (C₃-C₁₆)alkoxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, (C₆-C₁₄)aryl,(C₆-C₁₄)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₄)aryl,perfluoro(C₆-C₁₄)aryl(C₁-C₃)alkyl, (C₆-C₁₄)aryloxy,(C₆-C₁₄)aryl(C₁-C₆)alkoxy, tri(C₁-C₆)alkoxysilyl and a group of formula(A):—Z-Aryl  (A) wherein: Z is a bond or a group selected from the groupconsisting of: (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,(CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),(CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which may bethe same or different and each independently is 1 to 12; R₅ and R₆ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl, ethyl, linear or branched (C₃-C₆)alkyl,methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, (C₂-C₆)acyl,(C₂-C₆)acyloxy, phenyl and phenoxy; Aryl is phenyl or phenyl substitutedwith one or more of groups selected from the group consisting of methyl,ethyl, linear or branched (C₃-C₆)alkyl, hydroxy, methoxy, ethoxy, linearor branched (C₃-C₆)alkyloxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, phenyl andphenoxy; or one of R₁ or R₂ taken together with one of R₃ or R₄ and thecarbon atoms to which they are attached to form a (C₅-C₇)carbocyclicring optionally containing one or more double bonds; b) optionally oneor more monomers of formula (IV):

wherein R₁₆ and R₁₇ are the same or different and each independentlyselected from the group consisting of hydrogen, methyl, ethyl, linear orbranched (C₃-C₆)alkyl, methoxy, ethoxy, linear or branched(C₃-C₆)alkyloxy, acetoxy, (C₂-C₆)acyl, phenyl and phenoxy; or R₁₆ takentogether with R₁₇ and the carbon atoms to which they are attached toform a (C₅-C₇)carbocyclic ring optionally containing one or more doublebonds; R₁₈ is hydrogen, halogen, methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, hydroxy, methoxy,ethoxy, linear or branched (C₃-C₁₆)alkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, —O(CO)R₁₉ and —O(CO)OR₁₉, where R₁₉ ismethyl, ethyl, linear or branched (C₃-C₁₆)alkyl, (C₆-C₁₀)aryl and(C₆-C₁₀)aryl(C₁-C₆)alkyl; c) optionally one or more compounds selectedfrom the group consisting of: i) a compound of formula (VIIa):

ii) a compound of formula (VIIb):

 and iii) a compound of formula (VIIc):

where m is an integer 0, 1 or 2; b is an integer from 1 to 10; K isselected from the group consisting of CH₂, CH₂—CH₂, O and S; X isselected from the group consisting of O, S, NR_(a), SiR_(b)R_(c),SiR_(b)R_(c)O(SiR_(b)R_(c)O)_(n)SiR_(b)R_(c),SiR_(b)R_(c)(C₆-C₁₀)arylSiR_(b)R_(c), —C(O)—, —C(O)O—, —OC(O)—,—OC(O)—O—, —S—C(O)—, —C(O)—S—, —CH═CH— and —C≡C—; R_(a), R_(b) and R_(c)are independently of each other selected from the group consisting ofhydrogen, methyl, ethyl or a linear or branched (C₃-C₁₂)alkyl,(C₃-C₈)cycloalkyl, (C₅-C₁₂)bicycloalkyl, (C₅-C₁₂)bicycloalkenyl and(C₅-C₁₂)bicycloalkenyl(C₁-C₃)alkylSi(CH₃)₂, and such that O, NR_(a)and/or S atoms are not linked directly to one another; and n is aninteger from 0 to 10; d) an organo-ruthenium compound selected from thegroup consisting of: a compound of formula (IIB):

a compound of formula (IIIA):

a compound of formula (IIIB):

a compound of formula (IIIC):

1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium;wherein: X is a halogen or an anionic ligand; Y is selected from thegroup consisting of O and S; Y′ is OR₉ SR₉ and —N═CHC(O)O(C₁-C₆)alkyl,where R₉ is selected from the group consisting of methyl, ethyl, linearor branched (C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linear orbranched (C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy, —OCH(CH₃)C(O)N(CH₃)(OCH₃); L isPR₃ or O═PR₃, where R is independently selected from the groupconsisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl,bicyclo(C₅-C₁₀)alkyl, phenyl, benzyl, isopropoxy, sec-butoxy,tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy; or X and L form abidentate anionic ligand of the formula X-L; R₇ is selected from thegroup consisting of isopropyl, sec-butyl, tert-butyl, substituted orunsubstituted cyclohexyl, substituted or unsubstituted phenyl,substituted or unsubstituted biphenyl and substituted or unsubstitutednaphthyl; R₈ is selected from the group consisting of methyl, ethyl,linear or branched (C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linearor branched (C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy, —NHCO(C₁-C₆)alkyl,—NHCO-perfluoro(C₁-C₆)alkyl, —SO₂N((C₁-C₆)alkyl)₂ and —NO₂; Ar₁, Ar₂ Ar₃and Ar₄ are the same or different and each independently selected fromthe group consisting of substituted or unsubstituted phenyl, substitutedor unsubstituted biphenyl and substituted or unsubstituted naphthyl;wherein said substituents are selected from the group consisting ofmethyl, ethyl, iso-propyl, tert-butyl and phenyl; and e) a compound ofthe formula (V):

wherein Y is halogen; and R₃₀ and R₃₁ are the same or different andindependently of each other selected from hydrogen, methyl, ethyl,linear or branched (C₃-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)-aryloxy.
 15. The kit accordingto claim 14, which contains a compound of formula (V) selected from thegroup consisting of:

1-chloro-4-methoxy-9H-thioxanthen-9-one;

1-chloro-4-ethoxy-9H-thioxanthen-9-one;

1-chloro-4-propoxy-9H-thioxanthen-9-one (commercially sold under thename CPTX from Lambson);

1-chloro-2-propoxy-9H-thioxanthen-9-one;

1-chloro-2-ethoxy-9H-thioxanthen-9-one;

1-chloro-2-methoxy-9H-thioxanthen-9-one;

1-chloro-4-methyl-9H-thioxanthen-9-one;

1-chloro-4-ethyl-9H-thioxanthen-9-one;

1-bromo-4-propoxy-9H-thioxanthen-9-one; and

1-chloro-4-phenoxy-9H-thioxanthen-9-one.
 16. The kit according to claim14, which contains at least two monomers of formula (I) distinct fromone another, wherein one monomer is completely soluble in the othermonomer, and when said composition is exposed to radiation at 395 nm fora sufficient length of time it forms a three dimensional object.
 17. Thekit according to claim 14, which contains a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD),1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane(BisENBTMDS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).
 18. The kitaccording to claim 14, which contains a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD), 5-decylbicyclo[2.2.1]hept-2-ene (DecylNB),1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane(BisENBTMDS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).
 19. The kitaccording to claim 14, which contains a mixture of2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(PETD),1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane(BisENBHMTS),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)rutheniumand 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).
 20. A threedimensional object comprising the composition of claim 1.